Heterogeneous and homogeneous catalytic ozonation of benzothiazole promoted by activated carbon: kinetic approach

Ozone oxidation combined with activated carbon adsorption (O(3)/AC) has recently started to be developed as a single process for water and wastewater treatment. While a number of aspects of aqueous ozone decomposition are well understood, the importance and relationship between aqueous ozone decomposition and organic contaminant degradation in the presence of activated carbon is still not clear. This study focuses on determining the contribution of homogeneous and heterogeneous reactions to organic contaminants removal in O(3)/AC system. Benzothiazole (BT) was selected as a target organic pollutant due to its environmental concern. A reactor system based on a differential circular flow reactor composed by a 19 cm(3) activated carbon fixed bed column and 1 dm(3) storage tank was used. Ozone was produced from pure and dry oxygen using an Ozocav ozone generator rated at 5 g O(3)h(-1). Experimental results show that BT removal rate was proportional to activated carbon dosage. Activated carbon surface contribution to BT oxidation reactions with ozone, increased with pH in absence of radical scavengers. The radical reaction contribution within the pH range 2-11 accounted for 67-83% for BT removal in O(3)/AC simultaneous treatment. Results suggest that at pH higher than the pH of the point of zero charge of the activated carbon dissociated acid groups such as carboxylic acid anhydrides and carboxylic acids present on activated carbon surface could be responsible for the observed increase in the ozone decomposition reaction rate. A simplified mechanism and a kinetic scheme representing the contribution of homogeneous and heterogeneous reactions on BT ozonation in the presence of activated carbon is proposed.     

Interactions between copper and cadmium modify metal organ distribution in mature tilapia, Oreochromis mossambicus

Sexually mature female tilapia were exposed to sublethal concentrations of waterborne Cu and/or Cd over 6 days, and subsequent body concentrations of these metals were determined in several organs. The results show that the distribution of Cu and Cd was metal and organ specific. This is demonstrated, for example, by the observation that in tilapia, Cu exposure did not result in Cu accumulation in the liver, whereas in the intestinal wall, notably high concentrations of Cu and Cd were measured in metal exposed fish. In addition to single metal exposed fish, we also determined Cu and Cd body distribution in Cu?Cd co-exposed fish. The observed interactions in metal accumulation were most pronounced in the organs of fish exposed to low, environmentally realistic, metal concentrations.     

Black cherry growth response to ambient ozone and EDU

Field-grown black cherry (Prunus serotina Ehrh.) seedlings were treated with the antioxidant ethylenediurea (EDU) to evaluate height, diameter, and above-ground dry-weight biomass growth response to ambient ozone over four years. Nine blocks with 44 trees/block were used in a randomized complete block design with three foliar spray treatments: (1) 1000 ppm EDU mixed with a surfactant and water; (2) surfactant mixed with water; and (3) water only. In each growing season treatments were applied seven times at approximately 10-day intervals. Repeated measures analysis of variance indicated significant (P< or =0.05) treatment and year effects for log-transformed height and diameter growth over the four-year period. After four years, EDU-treated trees were approximately 17% taller and stem diameters were 21% greater than non-EDU-treated trees. Total above-ground dry-weight biomass at the end of four years was 47% greater for EDU-treated trees compared to non-EDU-treated trees.     

A comparison of the environmental impact of pesticide multiresidues and their occurrence in river waters surveyed by liquid chromatography coupled in tandem with UV diode array detection and mass spectrometry

Twenty-two pesticides and metabolites selected on the basis of a regional priority list, were surveyed in surface river waters by high performance liquid chromatography coupled in tandem with UV diode array detection and mass spectrometry, after an off-line pre-concentration step. Pesticide concentrations ranged between 0.07 and 4.8 microg/l according to the compound and sampling period. Analytical results were linked to the environmental risk of pesticides, evaluated by their system investigation of risk by integration of score (SIRIS) rank.     

Accelerated remediation of pesticide-contaminated soil with zerovalent iron

High pesticide concentrations in soil from spills or discharges can result in point-source contamination of ground and surface waters. Cost-effective technologies are needed for on-site treatment that meet clean-up goals and restore soil function. Remediation is particularly challenging when a mixture of pesticides is present. Zerovalent iron (Fe0) has been shown to promote reductive dechlorination and nitro group reduction of a wide range of contaminants in soil and water. We employed Fe0 for on-site treatment of soil containing > 1000 mg metolachlor, > 55 mg alachlor, > 64 mg atrazine, > 35 mg pendimethalin, and > 10 mg chlorpyrifos kg(-1). While concentrations were highly variable within the windrowed soil, treatment with 5% (w/w) Fe0 resulted in > 60% destruction of the five pesticides within 90 d and increased to > 90% when 2% (w/w) Al2(SO4)3 was added to the Fe0. GC/MS analysis confirmed dechlorination of metolachlor and alachlor during treatment. Our observations support the use of Fe0 for ex situ treatment of pesticide-contaminated soil.     

Vertical infiltration of fuel oil hydrocarbons in an agricultural soil

The influence of rainfall, air temperature and soil moisture on the vertical mobility in the soil of fuel oil hydrocarbons (HC) was investigated in a field experiment. A controlled spreading of fuel oil (nC10‐nC25) was performed at a rate of 5 L HCm^‐2 on an agricultural soil in summer and in winter. Concentration, chemical composition of HC and soil moisture were regularly determined at different soil depths between 0 and 140 cm, 1 h, 3, 8and 15 days (d) after the spreading of oil. Sorption of hydrocarbons onto the organo‐mineral matrix of the soil was studied in laboratory experiments. The results showed that in summer, with an air temperature of 24°C and without water leaching in the soil profile, 65% of the initial HC remained trapped in the 0–140 cm soil layer, about 20% of the HC volatilized and around 15% migrated deeper. A vertical selective migration of the lightest (nC10‐nC15) HC (naphthas) was shown lSd after the spreading of fuel oil. Naphthas progressively reached the 120–140 cm soil layers whereas the heavy fractions of oil (nC17‐nC25) migrated and concentrated in the 0–60 cm soil layers. In winter, when soil was regularly watered by rainfalls and at low air temperatures, only 47% of the initial HC remained in the 0–140 cm profile after 15 d. A fast vertical infiltration of naphthas occurred within the first 3 d. After 15 d, all HC were detected in the same relative amounts as in the initial oil in the whole profile. Volatilization was negligible in winter and an increase in the migration of total oil at depth in the soil profile was shown. As inferred from the laboratory experiments, the high soil moisture led to the decrease in HC sorption on the organo‐mineral matter of the soil.     

Quantification of metallothionein in whole body gammarus locusta (crustacea: amphipoda) using differential pulse polarography

A polarographic method was optimised for the quantitative determination of metallothionein (MT) in whole body Gammarus locusta (Crustacea: Amphipoda). The identity of the MT-like proteins was examined using electrophoretic analysis (SDS-PAGE) and induction studies (water-borne exposures to copper). The MT-method was then used to examine changes in MT levels over the lifetime (juveniles, sub-adults and adults) of a laboratory population of G. locusta; copper (Cu) and zinc (Zn) body burden were also measured by flame atomic absorption spectrometry. MT was quantified by heat-denaturation of 30?000?g supernatants (to remove the bulk of non-MT proteins) followed by differential pulse polarography (DPP) to measure sulphydryl-group containing proteins. DPP proved to be a sensitive and reliable method to quantify heat-stable total sulphydryl-proteins. The majority of the latter was indicated to be MT from SDS-PAGE and induction studies. SDS-PAGE revealed a putative MT of 23?±?0.6?kDa app. mol. wt., consistent with the average size of dimeric MTs (10–20?kDa) found in several aquatic invertebrate species. Copper-exposure revealed parallel increases in the amounts of 23?kDa protein and total sulphydryl-proteins. Levels of whole body MT (rabbit pure MT as standard) range between 1.3 and 2.3?mg?g^?1 dry wt. over the lifetime of G. locusta. Sex-related changes in MT status were observed, the levels in females being 1.6 times higher than in males (p<0.05). Copper and Zn body content changed over the lifetime of G. locusta, the levels in juveniles (p>0.05) and sub-adults (p<0.05) being higher than in adults. It is concluded that the inclusion of MT in ecotoxicological studies with amphipod crustaceans require some caution with respect to the stages of moulting and/or sexual maturation of organisms, but this should not provide any major impediment in its use in metal pollution monitoring.     

Speciation analysis of butyltin compounds in sediments of the Theoule harbour (France) by GC/AES

Over the last years, great progress in the research on speciation of butyltins has been made. Many coupling techniques have been successfully developed, with better applications to sediments samples in the environment. Sediments were collected from 1999 to 2000 to elucidate butyltin pollution in Theoule harbour. Most of the analysed samples showed evidence of butyltin compounds. The results show that the concentration of Tributyltin (TBT) was in the range 20–200?µg/kg in March 1999, 20–340?µg/kg in June 1999, 180–1280?µg/kg in July 2000, and 55–820?µg/kg in October 2000. A comparison of the MBT, DBT, and TBT results show that in 1999 the concentrations were in the order TBT?DBT?>?MBT, with some exceptions. The patterns observed in many sediment cores show a great disparity of organotin input concentration among the cores collected during one month and also during two different months, and from one season to the other. This paper provides information on the use of the acetic acid leaching system in the determination of butyltin. The method is applied to evaluate the occurrence of these species in sediments from the Theoule harbour, between 1999 and 2000. In this study, a GC/AES was applied, complemented with acetic acid leaching and monitored using two certified reference materials: PACS-2 reference sediment and BCR 462 (Report EUR 18406 EN, 1998).     

Speciation of heavy metals in Albanian coastal sediments

This article presents results on heavy metal (Fe, Mn, Cr, Ni, Cu, Cd, Pb and Zn) speciation in the coastal sediments of Albania. Sediment samples were collected within the framework of the activities of the Interreg Italia–Albania Project, carried out in the Southern Adriatic Sea in 2000–01. This study shows that Albanian coastal sediments are highly influenced by river input, as the decreasing concentrations from coast to offshore confirm. Pb represents an exception of the general trend; meteoric inputs are prevalent for this metal. Ni, Cr, Fe, Zn and Cu correlate significantly and positively in the entire area, indicating a common origin for these metals in the analyzed sediments. All metals result mostly associated to the most refractory phases, which constitute up to 80% of the total concentration. Nevertheless a recent input of Cr, Ni, Cu and Mn can be observed, as the result of mining and industrial activities, in some selected areas, such as the Drin Bay and Durres. Their high concentration in the bioavailable phase can determine toxic effect upon biota.